JP2001151915A - Polyolefinic, biaxially stretched, heat-shrinkable film - Google Patents
Polyolefinic, biaxially stretched, heat-shrinkable filmInfo
- Publication number
- JP2001151915A JP2001151915A JP33707499A JP33707499A JP2001151915A JP 2001151915 A JP2001151915 A JP 2001151915A JP 33707499 A JP33707499 A JP 33707499A JP 33707499 A JP33707499 A JP 33707499A JP 2001151915 A JP2001151915 A JP 2001151915A
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- Prior art keywords
- weight
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- resin
- film
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- Treatments Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は特に延伸安定性、厚
さムラ、透明性、シールカット性、熱収縮性が優れ、シ
ール時や焼却時の異臭が少ない、Ｌ型半折シール（以下
Ｌ字シール）包装機用に好適なポリオレフィン系二軸延
伸熱収縮性フィルムの提供に関する。BACKGROUND OF THE INVENTION The present invention relates to an L-shaped half-fold seal (hereinafter referred to as "L") which is particularly excellent in stretching stability, thickness unevenness, transparency, seal-cutting property and heat shrinkability, and has little unpleasant odor during sealing or incineration. The present invention relates to the provision of a polyolefin-based biaxially stretched heat-shrinkable film suitable for a packaging machine.
【０００２】[0002]
【従来の技術】従来Ｌ字シール包装分野は塩ビ系収縮フ
イルム、あるいはポリプロピレン系樹脂、ポリエチレン
系樹脂等からなる二軸延伸フィルムが使用されてきた。
しかしながら、塩ビ系フィルムはＬ字シール時や廃棄物
焼却時の塩酸ガス発生の問題があり、本質的に塩酸ガス
等の危害物質や異臭を発生しにくいポリオレフィン系樹
脂を主成分とした熱収縮性フィルムが近年要望されてい
る。ポリプロピレン系樹脂を使用した二軸延伸フィルム
は延伸安定性、シールカット性等は良好であるが、フィ
ルムの剛性が高くまた加熱収縮率も比較的小さい為、収
縮包装後に角（ツノ）と呼ばれる突起が出やすく、包装
仕上がりが十分満足できるものでない。2. Description of the Related Art Conventionally, in the field of L-shaped seal packaging, a PVC-based shrink film or a biaxially stretched film made of a polypropylene-based resin, a polyethylene-based resin or the like has been used.
However, PVC-based films have a problem of generating hydrochloric acid gas during L-shaped sealing and waste incineration, and are inherently heat-shrinkable mainly composed of harmful substances such as hydrochloric acid gas and polyolefin-based resins that do not easily generate off-flavors. Films have been desired in recent years. A biaxially stretched film using a polypropylene resin has good stretching stability and seal-cutting properties, but has a high rigidity and a relatively small heat shrinkage ratio. And the packaging finish is not fully satisfactory.
【０００３】ポリエチレン系樹脂を使用した二軸延伸フ
ィルムは一般的に延伸が困難であり、厚さムラも大き
く、延伸安定性に問題があるとともに熱間シール性が悪
く、Ｌ字シール部が口開きしやすい欠点を有している。
このポリエチレン系二軸延伸フィルムの欠点を解決する
方策として、原料樹脂にエチレン−酢酸ビニル共重合体
等を配合し、電子線等の高エネルギー線を照射した一般
的に架橋タイプと称するフィルムも提案されている（日
本国特許第１７３２４１８号、第１８４７３０６号）
が、本質的にエチレン−酢酸ビニル共重合体は酢酸臭等
の異臭が発生しやすい事及びシールカット性や耐ブロッ
キング性が十分でない問題点がある。またポリエチレン
系樹脂をポリプロピレン系樹脂でサンドイッチした構造
のフィルムも提案されているが、前記の中間的な品質に
とどまり、シールカット時に糸引が発生する等包装仕上
がりが十分でない。A biaxially stretched film using a polyethylene resin is generally difficult to stretch, has a large thickness unevenness, has a problem in stretching stability, has a poor hot sealing property, and has an L-shaped seal portion. It has the drawback of easy opening.
As a measure to solve the drawbacks of this polyethylene-based biaxially stretched film, a film generally called a cross-linking type that mixes raw material resin with ethylene-vinyl acetate copolymer and irradiates high energy rays such as electron beams is also proposed. (Japanese Patent Nos. 1732418 and 1847306)
However, essentially, the ethylene-vinyl acetate copolymer has a problem that an unpleasant odor such as an acetic acid odor is easily generated, and the seal cut property and the blocking resistance are not sufficient. A film having a structure in which a polyethylene resin is sandwiched by a polypropylene resin has also been proposed, but the quality is limited to the above-mentioned intermediate quality, and the packaging finish is not sufficient, for example, stringing occurs during seal cutting.
【０００４】[0004]
【発明が解決しようとする課題】本発明は上記したよう
な状況に鑑み、延伸安定性、厚さムラ、透明性、シール
カット性、熱収縮性が優れ、シール時や焼却時の異臭発
生が少ない、本質的にポリオレフィン系樹脂のみを使用
し、Ｌ字シール包装機用に好適なポリオレフィン系二軸
延伸熱収縮性フィルムの提供を目的とする。SUMMARY OF THE INVENTION In view of the above situation, the present invention is excellent in stretching stability, thickness unevenness, transparency, seal-cutting property, heat shrinkability, and has an unpleasant odor during sealing and incineration. An object of the present invention is to provide a polyolefin-based biaxially stretched heat-shrinkable film suitable for use in an L-shaped seal packaging machine, which uses a small amount of essentially a polyolefin-based resin.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、上記目的
のために鋭意検討を重ねた結果、特定のエチレン・αオ
レフィン共重合体樹脂を原料としたシートを特定の条件
下にて電子線照射して架橋後、二軸延伸することによ
り、上記目的を達成する熱収縮性フィルムを得ることを
見出し、本発明に到達した。Means for Solving the Problems The inventors of the present invention have conducted intensive studies for the above purpose, and as a result, have obtained a sheet made of a specific ethylene / α-olefin copolymer resin under a specific condition. The inventors have found that a heat-shrinkable film that achieves the above object can be obtained by biaxially stretching after crosslinking by irradiation with a ray, and the present invention has been achieved.
【０００６】本発明の第１の発明は、１９０℃における
メルトフローインデックス（以下ＭＩ）が２．０ｇ／１
０分以下であるエチレン・α−オレフィン共重合体樹脂
を８５重量％以上含むポリオレフィン系樹脂を原料とし
たシートの両面が電子線照射処理され、ゲル分率が５重
量％以下に架橋されている二軸延伸熱収縮性フィルムに
関するものである。本発明の第２の発明は、上記第１の
発明において共重合体樹脂のα−オレフィンがブテン−
１、ヘキセン−１、４−メチルペンテン−１、オクテン
−１の中から選ばれた少なくとも一種のα−オレフィン
であり、共重合体樹脂は密度が０．９２０ｇ／ｃｍ3以
下の成分を６０重量％以上含む熱収縮性フィルムに関す
るものである。The first invention of the present invention has a melt flow index (hereinafter referred to as MI) at 190 ° C. of 2.0 g / 1.
Both surfaces of a sheet made of a polyolefin-based resin containing 85% by weight or more of an ethylene / α-olefin copolymer resin for 0 minutes or less are subjected to electron beam irradiation, and the gel fraction is crosslinked to 5% by weight or less. It relates to a biaxially stretched heat-shrinkable film. The second invention of the present invention is the first invention, wherein the α-olefin of the copolymer resin is butene-
1, at least one α-olefin selected from hexene-1, 4-methylpentene-1 and octene-1, and the copolymer resin contains a component having a density of 0.920 g / cm 3 or less by 60% by weight. % Or more.
【０００７】本発明の第３の発明は、上記第１又は第２
の発明においてシートの構造が３層構造であり、中間層
の樹脂密度が表面層の樹脂密度より低い熱収縮性フィル
ムに関するものである。本発明の第４の発明は、上記第
１〜第３のいづれかの発明においてフィルムの１００℃
での無荷重時の加熱収縮率が縦、横方向ともに２５％以
上である熱収縮性フィルムに関するものである。本発明
の第５の発明は、上記第１〜第４のいづれかの発明にお
いてフィルムが環状シートからつくられた熱収縮性フィ
ルムに関するものである。[0007] The third invention of the present invention is the above-mentioned first or second invention.
The present invention relates to a heat-shrinkable film in which the sheet has a three-layer structure, wherein the resin density of the intermediate layer is lower than that of the surface layer. A fourth invention of the present invention is the method according to any one of the first to third inventions, wherein the film has a temperature of 100 ° C.
The heat-shrinkable film has a heat-shrinkage ratio of 25% or more in both the vertical and horizontal directions when no load is applied. The fifth invention of the present invention relates to a heat-shrinkable film in which the film is made of an annular sheet in any one of the first to fourth inventions.
【０００８】本発明の第６の発明は、１９０℃における
メルトフローインデックスが２．０ｇ／１０分以下であ
るエチレン・α−オレフィン共重合体樹脂を８５重量％
以上含むポリオレフィン系樹脂を原料としたシートを、
加速電圧が３００ＫＶ以下の低エネルギー電子線照射装
置にて電子線照射し、ゲル分率が５重量％以下に架橋後
二軸延伸する熱収縮性フィルムの製造方法に関するもの
である。本発明の第７の発明は、上記第６の発明におい
てフィルムが環状シートであり、環状シートの両面に電
子線照射し、ゲル分率を５重量％以下に架橋する請求項
６に記載された熱収縮性フィルムの製造方法に関するも
のである。In a sixth aspect of the present invention, an ethylene / α-olefin copolymer resin having a melt flow index at 190 ° C. of 2.0 g / 10 minutes or less is used in an amount of 85% by weight.
A sheet made from a polyolefin-based resin containing
The present invention relates to a method for producing a heat-shrinkable film which is irradiated with an electron beam by a low energy electron beam irradiation device having an acceleration voltage of 300 KV or less, crosslinked to a gel fraction of 5% by weight or less, and then biaxially stretched. A seventh invention of the present invention is described in the sixth invention, wherein the film is an annular sheet in the sixth invention, and both surfaces of the annular sheet are irradiated with an electron beam to crosslink the gel fraction to 5% by weight or less. The present invention relates to a method for producing a heat shrinkable film.
【０００９】[0009]
【発明の実施の形態】本明細書において「シート」はＴ
ダイやサーキュラーダイから押し出された延伸前のもの
をいい、「フィルム」は前記シートを延伸した後のもの
をいう。本発明におけるポリオレフィン系樹脂とはエチ
レン・α−オレフィン共重合体樹脂（以下ＬＬＤＰＥと
いう。）８５〜１００重量％と他の樹脂１５〜０重量％
の混合物をいう。ＬＬＤＰＥが８５重量％に満たないと
強度低下、シールカット性不良となり、本発明の目的を
達成することができない。他の樹脂は必要により、収縮
率アップ、低温収縮性改善、収縮応力改善など、本発明
の熱収縮性フィルムに付加的な性質を与えるために混合
される。他の樹脂としては、ポリエチレン、ＬＬＤＰＥ
以外のポリオレフィン樹脂、エチレン−酢酸ビニル共重
合体などがある。BEST MODE FOR CARRYING OUT THE INVENTION In the present specification, “sheet” is T
It refers to a sheet extruded from a die or a circular die before stretching, and “film” refers to a sheet after stretching the sheet. The polyolefin resin in the present invention is an ethylene / α-olefin copolymer resin (hereinafter referred to as LLDPE) in an amount of 85 to 100% by weight and another resin in an amount of 15 to 0% by weight.
Means a mixture of If LLDPE is less than 85% by weight, the strength is reduced and the seal cut property is poor, and the object of the present invention cannot be achieved. Other resins may be added as needed to provide additional properties to the heat shrinkable film of the present invention, such as increased shrinkage, improved low temperature shrinkage, improved shrinkage stress, and the like. Other resins include polyethylene, LLDPE
Other polyolefin resins, ethylene-vinyl acetate copolymers and the like.
【００１０】本発明のＬＬＤＰＥは、α−オレフィンの
コモノマーがいわゆるＣ４、Ｃ６、Ｃ８タイプのブテン
−１、ヘキセン−１、４−メチルペンテン−１、オクテ
ン−１の中から選ばれた少なくとも一種のＬＬＤＰＥで
あり、密度が０．９１０以下のの超低密度タイプのポリ
エチレン（以下ＶＬＤＰＥという。）やメタロセン系Ｌ
ＬＤＰＥも含む。ＬＬＤＰＥの１９０℃におけるＭＩ
は、２．０ｇ／１０分以下のものが好ましく、更には
０．５〜１．５ｇ／１０分のものが好適である。ＭＩが
２．０を越えるとシートの成形性が低下したり厚さムラ
が大きくなり、好ましくない。The LLDPE of the present invention is characterized in that the α-olefin comonomer is at least one selected from so-called C4, C6, C8 type butene-1, hexene-1,4-methylpentene-1 and octene-1. LLDPE, an ultra-low density type polyethylene having a density of 0.910 or less (hereinafter referred to as VLDPE) or metallocene L
Also includes LDPE. MI of LLDPE at 190 ° C
Is preferably 2.0 g / 10 min or less, more preferably 0.5 to 1.5 g / 10 min. If the MI exceeds 2.0, the moldability of the sheet decreases and the thickness unevenness increases, which is not preferable.
【００１１】本発明の熱収縮性フィルムは電子線照射処
理され、ゲル分率がフィルム重量の５重量％以下、好ま
しくは０．１〜３重量％に架橋されている。電子線照射
処理が強く、吸収線量の尺度としてのフィルムのゲル分
率が５重量％を超えるとフィルムの架橋度が上昇し、Ｌ
字シールカット性が悪くなり、包装仕上がりが劣る。ま
た全く架橋をしないと安定的に二軸延伸することが困難
であり、また延伸したフィルムの厚さムラやＬ字シール
の強度が弱く包装仕上がりが悪くなる。本発明において
はシートを電子線照射処理することによって架橋し、ゲ
ル分率を５重量％以下にする。電子線照射処理は加速電
圧３００ＫＶ以下で行なう必要があるが、加速電圧３０
０ＫＶ以下で処理してもゲル分率が５重量％を超えると
良い結果を得ることができない。The heat-shrinkable film of the present invention has been subjected to an electron beam irradiation treatment and crosslinked to a gel fraction of 5% by weight or less, preferably 0.1 to 3% by weight of the film weight. When the electron beam irradiation treatment is strong and the gel fraction of the film as a measure of absorbed dose exceeds 5% by weight, the degree of crosslinking of the film increases, and L
The character seal cut property is deteriorated, and the packaging finish is inferior. If no crosslinking is performed, stable biaxial stretching is difficult, and the thickness unevenness of the stretched film and the strength of the L-shaped seal are weak, resulting in poor packaging finish. In the present invention, the sheet is crosslinked by irradiating with an electron beam to reduce the gel fraction to 5% by weight or less. The electron beam irradiation process needs to be performed at an acceleration voltage of 300 KV or less.
Good results cannot be obtained if the gel fraction exceeds 5% by weight even if the treatment is carried out at 0 KV or less.
【００１２】ＬＬＤＰＥには、通常用いられるブロッキ
ング防止剤、滑剤、静電気防止剤、防曇剤、着色剤等を
配合しても良い。これらの添加剤は通常、ポリエチレン
系の樹脂に１〜２０％濃度程度に均一分散されたマスタ
ーバッチと呼ばれるもので配合されることが多く、配合
量は本来のＬＬＤＰＥの品質に影響を与えない範囲であ
ることが要求され、ポリオレフィン系樹脂１００重量％
に対し、15重量％以下である。マスターバッチに使用さ
れるポリエチレン系樹脂としては、線状低密度ポリエチ
レン樹脂（ＬＬＤＰＥ）や低密度ポリエチレン樹脂（Ｌ
ＤＰＥ）などが使用される。The LLDPE may be blended with commonly used antiblocking agents, lubricants, antistatic agents, antifogging agents, coloring agents and the like. These additives are usually blended in what is called a master batch uniformly dispersed in a polyethylene resin to a concentration of about 1 to 20%, and the blending amount is within a range that does not affect the original quality of LLDPE. 100% by weight of polyolefin resin
To 15% by weight or less. As the polyethylene resin used for the master batch, linear low density polyethylene resin (LLDPE) or low density polyethylene resin (L
DPE) is used.
【００１３】本発明においてＬＬＤＰＥは一種又は二種
以上の混合物であり、その密度は、０．９２０ｇ／ｃｍ
3以下の成分を６０重量％以上含むことが好ましく、更
には７５重量以上含むことが好適である。密度０．９２
０ｇ／ｃｍ3以下の成分が６０重量％未満となると収縮
仕上がり具合が大幅に低下する。ＬＬＤＰＥの密度の調
節は、共重合されるα−オレフィンの炭素数、割合など
を変化させることによって行なうことができる。In the present invention, LLDPE is one kind or a mixture of two or more kinds, and its density is 0.920 g / cm.
It is preferable to contain 60% by weight or more, and more preferably 75% or more, of 3 or less components. Density 0.92
When the content of 0 g / cm 3 or less is less than 60% by weight, the degree of shrinkage finish is significantly reduced. The density of LLDPE can be adjusted by changing the number of carbon atoms and the proportion of the α-olefin to be copolymerized.
【００１４】本発明のフィルムは単層、２層、３層、多
層等の構造をとることが出来る。３層以上の構造の場合
には、両表面層にはさまれた中間層の樹脂密度（混合系
の場合は加重平均値）が表面層の樹脂密度より低いこと
が必要である。表面層の樹脂密度が中間層より低い場合
は、フィルムの滑り性や耐ブロッキング性が劣り好まし
くない。本発明のフィルムは、その種類を限定されるこ
とはなく、Ｔダイ法によるものであっても環状シート法
によるものであっても良いが、環状シート法によるもの
が好ましい。The film of the present invention can have a single-layer, two-layer, three-layer, or multilayer structure. In the case of a structure having three or more layers, it is necessary that the resin density of the intermediate layer sandwiched between both surface layers (weighted average value in the case of a mixed system) is lower than the resin density of the surface layer. When the resin density of the surface layer is lower than that of the intermediate layer, the film has poor slipperiness and blocking resistance, which is not preferable. The type of the film of the present invention is not limited, and may be a T-die method or an annular sheet method, but is preferably an annular sheet method.
【００１５】また本発明のフィルムは、厚さ２００〜１
０００μｍのシートを面積倍率で２０〜４０倍延伸して
１０〜２５μｍのフィルムを得るものであり、延伸前に
実施する電子線架橋は加速電圧が３００ＫＶ以下、好ま
しくは２００〜３００ＫＶで行なう。加速電圧が３００
ＫＶ以上では、Ｌ字シールのカット性が悪く、好ましく
ない。これは加速電圧が３００ＫＶ以上ではシートの厚
さ方向に均一に照射されるので好ましいが、過剰に照射
すると架橋度が上昇しＬ字シールのカット性が不良にな
るのに対し、３００ＫＶ以下ではシートの厚さ方向に減
衰するため結果として架橋度が下がり、Ｌ字シールカッ
ト性が良くなるものと考えられる。電子線照射は環状シ
ートの場合には環状シートをフラットなテープ状として
シートの両面から、Ｔダイシートの場合にはシートの片
面から照射することが好ましい。The film of the present invention has a thickness of 200 to 1
A 000 μm sheet is stretched 20 to 40 times at an area magnification to obtain a 10 to 25 μm film, and electron beam crosslinking performed before stretching is performed at an acceleration voltage of 300 KV or less, preferably 200 to 300 KV. Acceleration voltage is 300
Above KV, the cutability of the L-shaped seal is poor, which is not preferable. This is preferable since the irradiation is uniformly performed in the thickness direction of the sheet when the accelerating voltage is 300 KV or higher. However, when the irradiation is excessive, the degree of crosslinking increases and the cutability of the L-shaped seal becomes poor. It is considered that the degree of cross-linking decreases as a result of the attenuation in the thickness direction, thereby improving the L-shaped seal cut property. In the case of an annular sheet, it is preferable to irradiate the electron beam from both sides of the sheet in the form of a flat tape and from the one side of the sheet in the case of a T-die sheet.
【００１６】二軸延伸時の面積延伸倍率については、２
０〜４０倍が好ましく、更には２５〜３５倍が好適であ
る。延伸倍率が２０倍未満では厚さムラが悪く、また収
縮率も低い。４０倍以上では、延伸時に破断が多発し安
定延伸出来ない。The area stretching ratio during biaxial stretching is 2
It is preferably from 0 to 40 times, more preferably from 25 to 35 times. If the stretching ratio is less than 20 times, the thickness unevenness is poor and the shrinkage ratio is low. If it is 40 times or more, breakage occurs frequently during stretching, and stable stretching cannot be performed.
【００１７】また収縮率については、１００℃での無荷
重時の加熱収縮率が縦、横方向ともに２５％以上が好ま
しく、更には３０％以上が好適である。１００℃での収
縮率が２５％未満では、シュリンク包装後にツノや皮皺
が目立ち包装仕上がりが不十分である。As for the shrinkage, the heat shrinkage under no load at 100 ° C. is preferably 25% or more, more preferably 30% or more in both the vertical and horizontal directions. If the shrinkage at 100 ° C. is less than 25%, horns and wrinkles are noticeable after shrink packaging, and the packaging finish is insufficient.
【００１８】[0018]
【実施例】以下、実施例に基づいて詳細に説明する。本
発明の下記実施例において延伸安定性、厚さムラ、ヘー
ズ、ゲル分率、熱収縮率、Ｌ字シール性、包装仕上がり
については下記の方法により評価を行った。 「延伸安定性」：通常のインフレ２軸延伸装置にて製膜
し、延伸開始点の変動を下記評点にて判定した。 ◎：ＰＰと同程度で非常に安定 ○：やや変動あるが問
題なし △：不安定も破断なし ×：不安定で破断発生
××：破断多発 「厚さムラ」：得られたフィルムの全幅を厚さ計で測定
しＲ値を算出した。 「ヘーズ」：ＡＳＴＭ Ｄ１００３に準拠して測定し
た。 「ゲル分率」：ＪＩＳ Ｋ６７６９に準拠して測定し
た。 「熱収縮率」：１００℃〜１３０℃のグリセリン浴に３
０秒浸漬した時の収縮率を測定した。 「Ｌ字シール性」及び「収縮仕上がり」：得られたフィ
ルムを３５０ｍｍ幅、長さ５００ｍの半折巻き取りに仕
上げ、協和電機製Ｌ字シーラー（ＴＣＡ４５０）にて市
販ティッシュペーパーのカートンを入れ、２００℃×
０．７秒の条件でシール後、Ｋ．Ｕ．システム製シュリ
ンクトンネル（ＭＳ５８４５５Ｓ）にて１４０℃で５秒
間の条件にて、収縮包装したものの外観を下記にて評価
した。 ◎：皮皺やツノが無く、またシール部も良好 ○：僅かな皮皺やツノがあるが、シールは良好であり商
品として合格 △：シールは良好であるが、皮皺やツノがやや目立ち商
品としては不合格 ×：シール穴あきや糸引きが発生、或いは皮皺、ツノが
目立ち商品としては不合格 耐ブロッキング性：上記半折巻き取りを４０℃にて４週
間放置後、下巻き部１０ｍについて上記と同様の包装テ
ストを実施し、開口性を下記にて評価した。 ◎：開口部を指先に挟み、１〜２回フィルムをもむこと
で簡単に２枚に分かれ、セパレーターガイドでの抵抗が
全くない。 ○：４〜５回フィルムをもむことで開口可能であり、上
記同様殆ど抵抗無く２枚に分かれ、セパレーターガイド
での抵抗も少ない。 △：粘着テープ等で開口部を開くことで開口可能である
が、２枚に分ける時に抵抗があり、セパレーターガイド
でフィルムにしわが時々入る。 ×：同上にて、セパレーターガイドできしみ音がしほぼ
連続的にシワが入り、フィルムが 破れる場合もある。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail based on embodiments. In the following Examples of the present invention, stretching stability, thickness unevenness, haze, gel fraction, heat shrinkage, L-shaped sealing property, and packaging finish were evaluated by the following methods. "Stretching stability": A film was formed with a normal inflation biaxial stretching apparatus, and the fluctuation of the stretching start point was determined by the following rating. ◎: Very stable at about the same level as PP ○: Slight fluctuation but no problem △: Unstable and no break ×: Unstable and break XX: Frequent break “Thickness unevenness”: The overall width of the obtained film The R value was calculated by measuring with a thickness gauge. "Haze": Measured according to ASTM D1003. "Gel fraction": Measured according to JIS K6769. “Heat shrinkage”: 3 in a glycerin bath at 100 ° C. to 130 ° C.
The shrinkage when immersed for 0 seconds was measured. "L-shaped sealability" and "shrinkage finish": The obtained film was finished into a half-folded roll having a width of 350 mm and a length of 500 m, and a carton of commercially available tissue paper was put in with an L-shaped sealer (TCA450) manufactured by Kyowa Denki. 200 ℃ ×
After sealing under the condition of 0.7 second, K.I. U. The external appearance of the shrink-wrapped product was evaluated in the following manner at 140 ° C. for 5 seconds in a shrink tunnel (MS58455S) manufactured by System Corporation. ：: No wrinkles and horns, and good seal part. 僅 か: Slight wrinkles and horns, but good seal and passed as a product. △: Good seal, but wrinkles and horns were slightly noticeable. Rejected as a product ×: Seal holes or stringing occurred, or skin wrinkles and horns were noticeable. Rejected as a product. The same packaging test as described above was performed for 10 m, and the opening property was evaluated as follows. ◎: The opening is sandwiched between fingertips, and the film is easily separated into two pieces by rubbing the film once or twice, and there is no resistance at the separator guide. ：: Opening is possible by peeling the film 4 to 5 times, and the film is divided into two pieces with almost no resistance as described above, and the resistance at the separator guide is small. Δ: The opening can be opened by opening the opening with an adhesive tape or the like, but there is resistance when divided into two sheets, and the film sometimes wrinkles with the separator guide. ×: In the same manner as above, the separator guide made a squeaking sound and almost continuously wrinkled, sometimes causing the film to be torn.
【００１９】実施例１ 両表面層樹脂としてＭＩが１．０、密度０．９２０のＬ
ＬＤＰＥ（ダウレックス２０４５ＡＣ）１００重量部に
ブロッキング防止剤として珪藻土１０重量％含有する低
密度ポリエチレン（以下ＬＤＰＥ）ベースマスターバッ
チ５重量部、滑剤としてエルシルアミド５重量％含有す
るＬＬＤＰＥベースマスターバッチ３重量部、中間層と
してＭＩが１．３、密度０．９１５のＬＬＤＰＥ（モア
テック０１２８Ｎ）１００重量部に滑剤として同上のＬ
ＬＤＰＥマスターバッチ３重量部を配合した樹脂を使用
し、各層の厚さの比（以下層比）が１／３／１となるよ
うにサーキュラーダイより押し出し急冷後、厚さ約３７
５μｍの３層環状シートを得た。このシートを２５０Ｋ
Ｖの加速電圧にて両面に５０ｋＧｙの電子線を照射後、
常法にて縦方向に５．１倍、横方向に４．９倍同時二軸
延伸し、厚さ約１５μｍのフィルムを得た。延伸安定
性、得られたフィルムの品質及びＬ字シール性、包装仕
上がり、耐ブロッキング性の評価結果を表１に示す。表
から明らかなように包装仕上がりは合格レベルであり、
耐ブロッッキングは非常に良好であった。Example 1 L having a MI of 1.0 and a density of 0.920 was used as a resin for both surface layers.
5 parts by weight of a low density polyethylene (hereinafter referred to as LDPE) base masterbatch containing 10% by weight of diatomaceous earth as an antiblocking agent, 3 parts by weight of an LLDPE base masterbatch containing 5% by weight of ercilamide as a lubricant, in 100 parts by weight of LDPE (Dawlex 2045AC) 100 parts by weight of LLDPE (moretech 0128N) having an MI of 1.3 and a density of 0.915 as an intermediate layer,
A resin mixed with 3 parts by weight of an LDPE master batch is extruded from a circular die so that the ratio of the thickness of each layer (hereinafter referred to as a layer ratio) becomes 1/3/1.
A 5-layer three-layer annular sheet was obtained. 250K
After irradiating both surfaces with an electron beam of 50 kGy at an acceleration voltage of V,
The film was simultaneously biaxially stretched by 5.1 times in the vertical direction and 4.9 times in the horizontal direction by a conventional method to obtain a film having a thickness of about 15 μm. Table 1 shows the evaluation results of the stretching stability, the quality of the obtained film, the L-shaped sealing property, the finished packaging, and the blocking resistance. As is clear from the table, the packaging finish is at the pass level,
Blocking resistance was very good.
【００２０】実施例２ 両表面層樹脂としてＭＩが１．３、密度０．９１５のＬ
ＬＤＰＥ（モアテック０１２８Ｎ）１００重量部に実施
例１と同一のブロッキング防止剤マスターバッチ５重量
部、滑剤マスターバッチ３重量部、中間層樹脂としてＭ
Ｉ１．５、密度０．８９５のメタロセン系ＬＬＤＰＥ
（アフィニティーＰＦ１１４０）１００重量部に実施例
１と同一の滑剤マスターバッチ３重量部を配合した樹脂
を使用し、表１に示す条件にて、実施例１と同様に二軸
延伸し、厚さ１５μｍのフィルムを得た。得られたフィ
ルムは１００℃の熱収縮率が３５％に向上し、包装仕上
がり、耐ブロッキング性も合格レベルであった。またこ
の包装品は柔らかな風合いの包装仕上がりであった。Example 2 L having a MI of 1.3 and a density of 0.915 was used as both surface layer resins.
5 parts by weight of the same antiblocking agent master batch as in Example 1, 3 parts by weight of a lubricant master batch, and 100 parts by weight of LDPE (Moortec 0128N)
Metallocene LLDPE with I1.5 and density 0.895
(Affinity PF1140) A resin prepared by blending 3 parts by weight of the same lubricant master batch as in Example 1 with 100 parts by weight was subjected to biaxial stretching in the same manner as in Example 1 under the conditions shown in Table 1 to a thickness of 15 μm. Was obtained. The heat shrinkage at 100 ° C. of the obtained film was improved to 35%, and the finished packaging and anti-blocking properties were also acceptable. The packaged product had a soft texture.
【００２１】実施例３ 両表面層樹脂は実施例２と同一とし、中間層樹脂として
ＭＩ１．５、密度０．８９５ののＬＬＤＰＥ（アフィニ
ティーＰＦ１１４０）７０重量部とＭＩ１．０、密度
０．９３０ののＬＬＤＰＥ（ダウレックス２０４２Ａ）
３０重量部に実施例１と同一の滑剤マスターバッチ３重
量部を配合した樹脂を使用し、層比１：３：１となるよ
うにサーキュラーダイより押し出し急冷し、厚さ約４８
０μｍの３層環状シートを得た。このシートを２８０Ｋ
Ｖの加速電圧にて両面に５０ｋＧｙの電子線を照射後、
常法にて縦方向に６．２倍、横方向に５．１倍同時二軸
延伸し、厚さ約１５μｍのフィルムを得た。このフィル
ムの品質は表１に示す様に、延伸安定性、厚さムラ、包
装仕上がり、耐ブロッキング性のバランスがとれており
実施例のなかでは最も好ましいものであった。Example 3 The resin for both surface layers was the same as in Example 2, and 70 parts by weight of LLDPE (affinity PF1140) having an MI of 1.5 and a density of 0.895 was used as an intermediate layer resin, and a resin having an MI of 1.0 and a density of 0.930 was used. LLDPE (Dawlex 2042A)
A resin prepared by mixing 3 parts by weight of the same lubricant master batch as in Example 1 with 30 parts by weight was extruded from a circular die so as to have a layer ratio of 1: 3: 1, and was quenched.
A 0 μm three-layer annular sheet was obtained. This sheet is 280K
After irradiating both surfaces with an electron beam of 50 kGy at an acceleration voltage of V,
Using a conventional method, the film was simultaneously biaxially stretched by 6.2 times in the longitudinal direction and 5.1 times in the transverse direction to obtain a film having a thickness of about 15 μm. As shown in Table 1, the quality of this film was balanced among stretching stability, thickness unevenness, finished packaging, and blocking resistance, and was the most preferable among the examples.
【００２２】比較例１ 表１に示す様に中間層樹脂のみＭＩ２．３、密度０．９
１７のＬＬＤＰＥ（ダウレックス２０４７ＡＣ）を使用
した他は実施例１と同一内容にて架橋・二軸延伸し、厚
さ約１５μｍのフィルムを得た。得られたフィルムは、
表１に示す通り厚さムラが大きく、また延伸が不安定で
あり、包装仕上がりも不合格であった。COMPARATIVE EXAMPLE 1 As shown in Table 1, only the intermediate layer resin had an MI of 2.3 and a density of 0.9.
Cross-linking and biaxial stretching were carried out in the same manner as in Example 1 except that LLDPE (Dawlex 2047AC) No. 17 was used to obtain a film having a thickness of about 15 μm. The resulting film is
As shown in Table 1, the thickness unevenness was large, the stretching was unstable, and the packaging finish was unacceptable.
【００２３】比較例２ 両表面層樹脂は、実施例２と同一とし、中間層樹脂とし
てＭＩ１．５、密度０．８９５のＬＬＤＰＥ（アフィニ
ティーＰＦ１１４０）３０重量部とＭＩ１．０、密度
０．９３０ののＬＬＤＰＥ（ダウレックス２０４２Ａ）
７０重量部に実施例１と同様の滑剤マスターバッチ３重
量部を配合した樹脂を使用し、層比１：３：１となるよ
うにサーキュラーダイより押し出し急冷し、厚さ約４８
０μｍの３層環状シートを得た。このシートを２８０Ｋ
Ｖの加速電圧にて両面に５０ｋＧｙの電子線を照射後、
常法にて縦方向に６．２倍、横方向に５．１倍同時二軸
延伸し、厚さ約１５μｍのフィルムを得た。このフィル
ムの品質は表１に示す様に、１００℃での熱収縮率が低
下してしまい包装仕上がりは不合格であった。COMPARATIVE EXAMPLE 2 Both surface layer resins were the same as those in Example 2, and 30 parts by weight of LLDPE (affinity PF1140) having an MI of 1.5 and a density of 0.895 were used as an intermediate layer resin, and a resin having an MI of 1.0 and a density of 0.930 was used. LLDPE (Dawlex 2042A)
A resin prepared by mixing 3 parts by weight of the same lubricant master batch as in Example 1 with 70 parts by weight was extruded from a circular die so as to have a layer ratio of 1: 3: 1, and was quenched.
A 0 μm three-layer annular sheet was obtained. This sheet is 280K
After irradiating both surfaces with an electron beam of 50 kGy at an acceleration voltage of V,
Using a conventional method, the film was simultaneously biaxially stretched by 6.2 times in the longitudinal direction and 5.1 times in the transverse direction to obtain a film having a thickness of about 15 μm. As shown in Table 1, the quality of this film was such that the heat shrinkage at 100 ° C. was reduced, and the packaging was rejected.
【００２４】比較例３ 実施例３と同一樹脂配合、厚さ、層比にて得られた環状
シートを４００ＫＶの加速電圧にて両面に５０ｋＧｙの
電子線を照射後、常法にて縦方向に６．２倍、横方向に
５．１倍同時二軸延伸し、約１５μｍのフィルムを得
た。このフィルムの品質は表１に示す様に延伸安定性、
熱収縮率は実施例３と同等以上であったが、ゲル分率が
５．６重量％と高く、Ｌ字シール時に糸引きが発生し、
包装仕上がりは不合格であった。Comparative Example 3 An annular sheet obtained with the same resin composition, thickness and layer ratio as in Example 3 was irradiated with an electron beam of 50 kGy on both sides at an accelerating voltage of 400 KV, and then vertically oriented in a conventional manner. The film was simultaneously biaxially stretched 6.2 times and 5.1 times in the transverse direction to obtain a film of about 15 μm. The quality of this film is as shown in Table 1, stretching stability,
Although the heat shrinkage was equal to or higher than that of Example 3, the gel fraction was as high as 5.6% by weight, and stringing occurred during L-shaped sealing.
The packaging finish was rejected.
【００２５】表１から明らかな様に、本発明に係る熱収
縮性多層フィルムは、本質的にＬＬＤＰＥからなり、延
伸性が良く、厚さムラが少なく、透明性、包装仕上が
り、耐ブロッキング性に優れるものである。As is clear from Table 1, the heat-shrinkable multilayer film according to the present invention consists essentially of LLDPE, has good stretchability, has small thickness unevenness, and has excellent transparency, packaging finish, and blocking resistance. It is excellent.
【００２６】[0026]
【表１】 [Table 1]
【００２７】[0027]
【発明の効果】本発明の熱収縮性フィルムは、延伸性が
良く、厚さムラが少なく、透明性、包装仕上がり、耐ブ
ロッキング性に優れるＬ字シーラー等で使用される熱収
縮包装に好適なフィルムである。更に、原料樹脂として
本質的にポリオレフィン系樹脂からなるため、塩化ビニ
ル系フィルムやエチレン−酢酸ビニル共重合体を配合し
たフィルムに比べ、シール時や廃棄物焼却時に異臭等の
環境負荷が少ない優れた特性をもつ包装産業用に好適な
フィルムである。The heat-shrinkable film of the present invention is suitable for heat-shrinkable packaging used in an L-shaped sealer or the like which has good stretchability, has small thickness unevenness, and is excellent in transparency, packaging finish and blocking resistance. Film. Furthermore, since it is essentially composed of a polyolefin resin as a raw material resin, it has an excellent environmental load such as an unpleasant odor at the time of sealing or waste incineration as compared with a vinyl chloride film or a film containing an ethylene-vinyl acetate copolymer. It is a film suitable for the packaging industry having characteristics.
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） // Ｃ０８Ｊ 5/18 ＣＥＳ Ｃ０８Ｊ 5/18 ＣＥＳ Ｂ２９Ｋ 23:00 Ｂ２９Ｋ 23:00 Ｂ２９Ｌ 7:00 Ｂ２９Ｌ 7:00 9:00 9:00 Ｃ０８Ｌ 23:08 Ｃ０８Ｌ 23:08 Ｆターム(参考） 4F071 AA15 AA15X AA21 AA21X AA82 AA88 AF61 AH04 BB08 BB09 BC01 BC05 4F073 AA05 BA07 BB01 BB03 CA42 4F100 AK06 AK62A AK62B AK62C AK63 AK65A AK65B AK65C AK66A AK66B AK66C BA03 BA06 BA10A BA10C BA16 EJ38A EJ38B EJ38C EJ53A EJ53B EJ53C GB15 JA03A JA03B JA03C JA06A JA06B JA06C JA13A JA13B JA13C JK08 JN01 YY00A YY00B YY00C 4F210 AA04E AA09 AE01 AG01 AG03 RC02 RG02 RG04 RG09 RG43 Continued on the front page (51) Int.Cl. 7 Identification FI FI Theme Court II (Reference) // C08J 5/18 CES C08J 5/18 CES B29K 23:00 B29K 23:00 B29L 7:00 B29L 7:00 9: 00 9:00 C08L 23:08 C08L 23:08 F term (reference) 4F071 AA15 AA15X AA21 AA21X AA82 AA88 AF61 AH04 BB08 BB09 BC01 BC05 4F073 AA05 BA07 BB01 BB03 CA42 4F100 AK06 AK62A AK62B AK62B AK62B AK62B BA10A BA10C BA16 EJ38A EJ38B EJ38C EJ53A EJ53B EJ53C GB15 JA03A JA03B JA03C JA06A JA06B JA06C JA13A JA13B JA13C JK08 JN01 YY00A YY00B YY00C 4F210 AA04E AA09 AE01 AG01 RG04 RC04
Claims (7)
スが２．０ｇ／１０分以下であるエチレン・α−オレフ
ィン共重合体樹脂を８５重量％以上含むポリオレフィン
系樹脂を原料としたシートの両面あるいは片面が電子線
照射処理され、ゲル分率が５重量％以下に架橋されてい
る二軸延伸熱収縮性フィルム。1. A sheet made of a polyolefin resin containing 85% by weight or more of an ethylene / α-olefin copolymer resin having a melt flow index at 2.0 ° C. of 2.0 g / 10 minutes or less at 190 ° C. A biaxially stretched heat-shrinkable film which has been subjected to line irradiation and crosslinked to a gel fraction of 5% by weight or less.
１、ヘキセン−１、４−メチルペンテン−１、オクテン
−１の中から選ばれた少なくとも一種のα−オレフィン
であり、共重合体樹脂は密度が０．９２０ｇ／ｃｍ3以
下の成分を６０重量％以上含む請求項１に記載された熱
収縮性フィルム。2. The copolymer resin of claim 1 wherein the α-olefin is butene-
1, at least one α-olefin selected from hexene-1, 4-methylpentene-1 and octene-1, and the copolymer resin contains a component having a density of 0.920 g / cm 3 or less by 60% by weight. %.
樹脂密度が表面層の樹脂密度より低い請求項１又は請求
項２に記載された熱収縮性フィルム。3. The heat-shrinkable film according to claim 1, wherein the sheet has a three-layer structure, and the resin density of the intermediate layer is lower than the resin density of the surface layer.
縮率が縦、横方向ともに２５％以上である請求項１〜請
求項３のいづれかに記載された熱収縮性フィルム。4. The heat-shrinkable film according to claim 1, wherein the heat shrinkage of the film at 100 ° C. when no load is applied is 25% or more in both the vertical and horizontal directions.
項１〜請求項４のいづれかに記載された熱収縮性フィル
ム。5. A heat-shrinkable film according to claim 1, wherein the film is made from an annular sheet.
スが２．０ｇ／１０分以下であるエチレン・α−オレフ
ィン共重合体樹脂を８５重量％以上含むポリオレフィン
系樹脂を原料としたシートを、加速電圧が３００ＫＶ以
下の低エネルギー電子線照射装置にて電子線照射し、ゲ
ル分率を５重量％以下に架橋後二軸延伸する熱収縮性フ
ィルムの製造方法。6. A sheet prepared from a polyolefin-based resin containing 85% by weight or more of an ethylene / α-olefin copolymer resin having a melt flow index at 190 ° C. of 2.0 g / 10 minutes or less at an accelerating voltage of 300 KV. A method for producing a heat-shrinkable film which is irradiated with an electron beam by the following low energy electron beam irradiation device, crosslinked to a gel fraction of 5% by weight or less, and then biaxially stretched.
両面に電子線照射し、ゲル分率を５重量％以下に架橋す
る請求項６に記載された熱収縮性フィルムの製造方法。7. The method for producing a heat-shrinkable film according to claim 6, wherein the sheet is an annular sheet, and both sides of the annular sheet are irradiated with an electron beam to crosslink the gel fraction to 5% by weight or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33707499A JP2001151915A (en) | 1999-11-29 | 1999-11-29 | Polyolefinic, biaxially stretched, heat-shrinkable film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33707499A JP2001151915A (en) | 1999-11-29 | 1999-11-29 | Polyolefinic, biaxially stretched, heat-shrinkable film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001151915A true JP2001151915A (en) | 2001-06-05 |
Family
ID=18305198
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33707499A Pending JP2001151915A (en) | 1999-11-29 | 1999-11-29 | Polyolefinic, biaxially stretched, heat-shrinkable film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001151915A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003136653A (en) * | 2001-11-01 | 2003-05-14 | Kohjin Co Ltd | Polyethylenic crosslinked shrink film |
| JP2004207341A (en) * | 2002-12-24 | 2004-07-22 | Sanken Electric Co Ltd | Emitted light wavelength converting semiconductor light emitting device and its manufacturing method |
| JP2006257129A (en) * | 2005-03-15 | 2006-09-28 | Okura Ind Co Ltd | Polyethylene-based tubular biaxially oriented film |
| WO2007032306A1 (en) * | 2005-09-15 | 2007-03-22 | Asahi Kasei Chemicals Corporation | Thermally shrinkable multilayer sheet |
| JP2018515633A (en) * | 2015-03-18 | 2018-06-14 | ダウ グローバル テクノロジーズ エルエルシー | Protective film, blend, and production method thereof |
| JP2018111319A (en) * | 2018-04-03 | 2018-07-19 | 旭化成株式会社 | Polyethylene-based crosslink shrink film |
-
1999
- 1999-11-29 JP JP33707499A patent/JP2001151915A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003136653A (en) * | 2001-11-01 | 2003-05-14 | Kohjin Co Ltd | Polyethylenic crosslinked shrink film |
| JP2004207341A (en) * | 2002-12-24 | 2004-07-22 | Sanken Electric Co Ltd | Emitted light wavelength converting semiconductor light emitting device and its manufacturing method |
| JP2006257129A (en) * | 2005-03-15 | 2006-09-28 | Okura Ind Co Ltd | Polyethylene-based tubular biaxially oriented film |
| WO2007032306A1 (en) * | 2005-09-15 | 2007-03-22 | Asahi Kasei Chemicals Corporation | Thermally shrinkable multilayer sheet |
| JPWO2007032306A1 (en) * | 2005-09-15 | 2009-03-19 | 旭化成ケミカルズ株式会社 | Heat shrinkable multilayer film |
| JP4954882B2 (en) * | 2005-09-15 | 2012-06-20 | 旭化成ケミカルズ株式会社 | Heat shrinkable multilayer film |
| JP2018515633A (en) * | 2015-03-18 | 2018-06-14 | ダウ グローバル テクノロジーズ エルエルシー | Protective film, blend, and production method thereof |
| JP2018111319A (en) * | 2018-04-03 | 2018-07-19 | 旭化成株式会社 | Polyethylene-based crosslink shrink film |
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